N-[2-({[1-(4-Chloro­phen­yl)-1H-pyrazol-3-yl]­oxy}meth­yl)phen­yl]-N-meth­oxy­hydrazinecarboxamide

Rajni Kant; Vivek K Gupta; Kamini Kapoor; Chetan S Shripanavar; Kaushik Banerjee

doi:10.1107/S1600536812038214

. 2012 Sep 12;68(Pt 10):o2916. doi: 10.1107/S1600536812038214

N-[2-({[1-(4-Chlorophenyl)-1H-pyrazol-3-yl]oxy}methyl)phenyl]-N-methoxyhydrazinecarboxamide

Rajni Kant ^a, Vivek K Gupta ^a, Kamini Kapoor ^a, Chetan S Shripanavar ^b, Kaushik Banerjee ^b,^*

PMCID: PMC3470263 PMID: 23125707

Abstract

In the title compound, C₁₈H₁₈ClN₅O₃, the hydrazinecarboxamide N—N—C(O)—N unit is nearly planar [maximum deviation = 0.074 (2) Å] and is inclined at a dihedral angle of 57.43 (7)° with respect to the plane of the attached benzene ring. The chlorophenyl group makes dihedral angles of 19.71 (7) and 34.07 (6)° with the pyrazole and benzene rings, respectively. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion dimers that are further linked into chains along the a-axis direction by N—H⋯N hydrogen bonds. In addition, π–π stacking interactions are observed between benzene rings [centroid–centroid distance = 3.680 (1) Å].

Related literature

For the biological activity of pyraclostrobin (systematic name: methyl N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}), see: Esteve-Turrillas et al. (2011 ▶); Mercader et al. (2008 ▶); Patel et al. (2012 ▶). For a related structure, see: Attia et al. (2012 ▶).

Experimental

Crystal data

C₁₈H₁₈ClN₅O₃
M _r = 387.82
Monoclinic,
a = 7.6830 (4) Å
b = 9.1597 (4) Å
c = 26.1083 (12) Å
β = 91.683 (4)°
V = 1836.55 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.832, T _max = 1.000
27359 measured reflections
3616 independent reflections
2922 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.112
S = 1.12
3616 reflections
256 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812038214/gk2517sup1.cif

e-68-o2916-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038214/gk2517Isup2.hkl

e-68-o2916-Isup2.hkl^{(173.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812038214/gk2517Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H51⋯N6ⁱ	0.88 (2)	2.28 (2)	3.080 (3)	153 (2)
N6—H61⋯O1ⁱⁱ	0.86 (2)	2.34 (2)	3.120 (3)	152 (2)
N6—H62⋯N15ⁱⁱ	0.87 (3)	2.56 (3)	3.408 (3)	164 (2)

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

RK acknowledges the Department of Science & Technology for access to the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003.

supplementary crystallographic information

Comment

Pyraclostrobin, which belongs to the latest generation of strobilurin family of fungicides, shows a broad antifungal activity spectrum and higher efficiency and security profiles than previous fungicides (Patel et al., 2012; Esteve-Turrillas et al., 2011; Mercader et al., 2008).

In the title compound all bond lengths and angles are normal and correspond to those observed in the related structure (Attia et al., 2012). The hydrazinecarboxamide moiety (N2,N5,N6/O1/C1) is nearly planar with a maximum deviation of 0.074 (2) Å at atom N6, and is inclined at an angle of 57.43 (7)° with the benzene ring (C7–C12). The dihedral angle between the benzene rings is 34.07 (6)°. Chlorophenyl group makes a dihedral angle of 19.71 (7)° with the pyrazole ring. In the crystal, N6—H61···O1 hydrogen bonds link pairs of molecules to form inversion dimers and dimers are connected via N6—H62···N15 and N5—H51···N6 hydrogen bonds to form chains along the a axis of the unit cell (Table 1, Fig. 2). The crystal structure is further stabilized by π–π interactions between the benzene ring (C19—C24) of the molecule at (x, y, z) and the benzene ring of an inversion related molecule at (- x, 1 - y, -z)[centroid separation = 3.680 (1) Å, interplanar spacing = 3.396 Å and centroid shift = 1.41 Å].

Experimental

Pyraclostrobin (0.373 g, 0.001 mol) was dissolved in 5 ml methanol and to it hydrazine hydrate (0.1 g, 0.002 mol) solution was added and refluxed at 70°C for 1 h. The reaction mixture was then cooled and compound was separated out by removal of the solvent under reduced pressure. The product was dissolved in methanol and kept for slow evaporation of solvent to get crystals of the title compound (m.p. 398 K).